Patent GB-1062756-A (GB)
Title: Polyesters
IPC: C08G63/58
Filed: 1963-10-31
Abstract: Polyesters containing pendant haloalkyl groups are made by reacting (a) an organic dicarboxylic acid or anhydride thereof, and (b) a vicinal alkylene oxide containing three or four carbon atoms and having attached to a carbon atom of the oxirange ring a methyl group or ethyl group substituted by two or more fluorine, chlorine or bromine atoms.  Up to 50% by weight of the alkylene oxide may be replaced by a second vicinal alkylene oxide which are on either or both of the carbon atoms if the oxirane ring is unsubstituted or is substituted by one or two C1-C2 alkyl or alkoxy groups, and one of these groups may be substituted by one fluorine, chlorine or bromine atom.  The dicarboxylic acid may be malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, perfluorosuccinic, perfluoroglutaric, perfluoroadipic, tetrahydrophthalic, hexahydroterephthalic, chlorendic, phthalic, isophthalic, terephthalic, maleic, fumaric, chloromaleic, itaconic or mixtures. Reaction is effected by heating, possibly in the presence of a diluent or under pressure.  Catalysts for the reaction are various halides or alkoxides of B, Al, Sb, Sn, Ti or Fe; complexes of FriedelCrafts catalysts with a dicarboxylic acid; formates of Zn, Al or Sn; tin oxalate, PhO and tertiary amines.  Polyesters derived from an ethylenically unsaturated dicarboxylic acid may be mixed with an unsaturated compound, e.g. a conventional monomer containing one or more double bonds or a natural or synthetic rubber and the mixture then cross-linked with a conventional vinyl polymerization catalyst and, possibly, an initiator.  The mixture may also contain a conventional unsaturated polyester or a plasticizer (e.g. an ester), filler, stabilizer, lubricant or antioxidant e.g. an organic phosphite. The polyesters, especially if unsaturated, may be admixed with a drying oil to form a coating composition.  In examples polyesters were made by reacting (1)-(9) maleic anhydride and 3,3,3-trichloropropylene oxide or 3,3-dichloropropylene oxide; (10) maleic anhydride, 3,3,3 - trichloropropylene oxide and 3,3 - dichloropropylene oxide; (11) maleic anhydride and 3,3,3-trichloropropylene oxide and propylene oxide; (12) maleic anhydride and 1,1,1 - trichloro - 3,4 - epoxybutane; (13) maleic anhydride and 3-bromo-3,3-dichloropropylene oxide; (14) fumaric acid and 3,3,3 - trichloropropylene oxide; (15) itaconic acid and 3,3-dichloropropylene oxide; (16) maleic anhydride, phthalic anhydride and 3,3-dichloropropylene oxide; (17) maleic anhydride, fumaric acid and 3,3,3-trichloropropylene oxide. In Examples (18)-(37) various of these polyesters were cross-linked with styrene, triallyl isocyanurate, diallyl phthalate, vinyl toluene, butyl methacrylate, a mixture of styrene and methyl methacrylate or a mixture of styrene and butyl methacrylate.  In examples (38) a mixture of a maleic anhydride-dichloro propylene oxide polyester, a styrene-butadiene rubber, furnace black, zinc oxide, sulphur, 2-mercaptobenzothiazole and phenyl-beta-naphthylamine were milled together and the mixture cured. In Example (39) a mixture of a polyester of 1,2-propanediol, phthalic anhydride and maleic anhydride and a polyester of maleic anhydride and trichloropropylene oxide was dissolved in styrene and cured.